Silicon

https://doi.org/10.1007/s12633-018-9847-7

ORIGINAL PAPER

Development and Characterization of Inorganic-Organic (Si-O-Al)

Hybrid Geopolymeric Precursors via Solid State Method
Rainy Gupta1,2 · Pooja Bhardwaj1,2 · Kumud Deshmukh2 · Deepti Mishra2 · Murari Prasad1,2 ·
Sudhir S. Amritphale1,2

Received: 15 October 2017 / Accepted: 3 April 2018

© Springer Science+Business Media B.V., part of Springer Nature 2018

Abstract
In this study, an innovative one part, solution free concept applied for the development of hybrid inorganic–organic
geopolymeric precursors having Si-O-Al networks at the precursor stage only. For the process development, fly ash, sodium
hydroxide along with rice husk were together mechano-chemically dry grinded for a period of 8, 16 and 24 hours and
‘organic in-organic hybrid geopolymeric precursors’ in solid powder form is obtained. Mechanico-chemically derived
tailored organic in-organic hybrid geopolymeric precursors were characterized by different techniques like XRD, 29 Si MAS
NMR, 27 Al MAS NMR, SEM and FESEM. XRD results revealed presence of inorganic phases and organic phase in organic
in-organic hybrid geopolymeric precursors. 29 Si MAS NMR spectra revealed partial transformation of tertracoordinated Si
into pentacoordinated silica due to presence of organic moiety.27 Al MAS NMR spectra indicated presence of peaks centered
at δ 52 to δ 66 ppm confirmed the formation of geopolymeric precursors. Developed geopolymeric precursor overcome
the process drawbacks of conventional geopolymerization process via solution chemistry by making it user friendly as
geopolymer from these geopolymeric precursor is obtained by addition of water only unlike conventional geopolymerization
process which involves addition of hazardous alkaline solution to aluminosilicate raw material like fly ash. Further, the
development of geopolymeric precursor utilize two environmentally unsafe waste materials and resulted in development of
material with improved mechanical properties.

Keywords Solution free · Mechanochemically · Fly ash · Silica · Precursors

1 Introduction functional groups but also presents a greener way in their

From development point of view today, inorganic-organic
hybrid materials are fascinating and alternatives for several
unusual applications. The formation of composites using
properties of both inorganic and organic compounds make
it possible to control performances of the end products. In
this context, careful selection of different raw materials is
utmost need which not only provide inorganic and organic
 Deepti Mishra
deeptimishrampri@gmail.com
1
Academy of Scientific and Innovative
Research-AcSIR-AMPRI, Bhopal, India
2
Materials for Radiation Shielding and Cement Free Concrete
Division, CSIR-AMPRI (Advanced Materials and Processes
Research Institute), Hoshangabad Road, Bhopal (M.P.)
462064, India
synthesis with controllable and tailored properties of end
products [1].
Geopolymers, contain strong three dimensional network
of Si-O-Si and Si-O-Al type bonds in structure, prepared by
alkali activation of different silica and alumina containing
raw materials at different ambient and elevated tempera-
tures. This strong silicate and aluminate network provide
geopolymers with excellent strength, durability, mechanical
properties with eco-friendly nature and greener production
characteristics. Geopolymeric material are well suited for
broad range low tech and high tech commercial applica-
tions i.e. from construction to air craft cabin materials [2–5].
Previous studies on geopolymers focused on the dissolu-
tion of glassy silicoaluminous phase from the raw materials
(fly ash, red mud, rice husk ash, metakaolin, slag etc.) in
a highly aqueous alkaline solution comprising of sodium
hydroxide with or without sodium silicate [6–10]. How-
ever, from the literature survey, it is clear that the current

geopolymerization technology suffers from drawbacks of
i) use of aqueous, highly hazardous and alkaline sodium
hydroxide solution and ii) use of untailored raw materials
leading to unpredictable properties, inhibiting the techno-
commercial viability of the process and iii)formation of
non-uniform geopolymer matrix resulting in brittle nature
of end products. Different researchers formulated one part
geopolymeric mixes by only physical mixing and blending
of all raw materials but again the drawbacks of the process
are either highly energy intensive process or limited avail-
ability of required raw materials and costly chemicals or
the geopolymeric end products exhibited negligible strength
making it unfit for any construction purposes [11–14].
In order to attain desired functional properties, hybrid
geopolymers introduced which arobtained by hybridiz-
ing organic polymer with geopolymeric matrix. Recently,
researchers have reported synthesis of novel hybrid organic
geopolymeric material prepared by co-reticulation of epoxy
based hybrid resin with metakaolin based geopolymer inor-
ganic matrix [15]. With the aim to enhance fire resistant
properties of organic polymers, a new geopolymeric com-
posite developed with epoxy organic matrix [16, 17]. By
incorporating inorganic and organic matrix, geopolymeric
materials with excellent fire protection and mechanical
properties were obtained.
Fig. 1 Raw materials and schematic solid state methodology for the formation of advanced organic in-organic hybrid geopolymeric precursor
material
Silicon
In view of this, current study presents an innovative,
one part risk free process for the synthesis of tailored
organic in-organic hybrid geopolymeric precursor material
by together mechano-chemical grinding of two abundantly
found environmentally unsafe waste materials i.e. fly ash,
as source of glassy inorganic silica and alumina and rice
husk as source of organic cellulose, hemicellulose and lignin
and sodium hydroxide in ball mill for grinding duration of
8, 16 and 24 hours following solid state chemistry route.
The scheme of novel solid state methodology with raw
materials for the work is shown in Fig. 1. The research
question for the current study was to observe the effect
of mechanochemical grinding for prolonged hours on the
geopolymeric raw materials and to well characterize the
mechanochemically developed solid powder material as
geopolymeric precursors having organic in-organic hybrid
characters. Developed tailored organic in-organic hybrid
solid geopolymeric precursor material then subjected to
X-ray diffraction, 29 Si and 27 Al MAS Nuclear magnetic
Resonance (NMR), Scanning electron microscopy and Field
Emission scanning Electron Microscopy (FESEM) analysis.
Continuous mechano-chemical grinding induced amor-
phization, increase the surface area and fineness of fly ash.
Several research studies reported that grinding of minerals
e.g. fly ash resulted in disordering and failure of crystalline
Silicon
portion and induced amorphization [18, 19]. On the other
hand, mechanical activation of fly ash resulted in increased
pozzolanic activity and high mechanical performance [20,
21].
2 Experimental Work
2.1 Raw Materials and Mechanochemical Grinding
ASTM C618 class F fly ash from DIRK India Private lim-
ited used for the study. Rice husk and fly ash were dried well
in hot air oven (60 ◦ C) prior to ball mill grinding. Sodium
hydroxide pellets procured from Rankem Co. with 98%
purity and used as alkali activator. As per DIRK specifica-
tions, fly ash contain 90±2% of SiO2 +Al2 O3 +Fe2 O3, CaO
5.0±0.5%, MgO 4.0±0.5% and Na2 O 1.5±0.2%. The
particle fineness and particle size of fly ash were 310-
325 m2 /kg and 7±4 µrespectively. Chemically unburnt rice
husk contain cellulose 35%, hemicellulose 25%, lignin 20%
alongwith amorphous silica 16%.The formulation acquired
for the study composed of fly ash 88.4% rice husk 0.38%
and sodium hydroxide 10.7% by weight Raw materials
together subjected to mechanochemical grinding in a ball
mill (10kg capacity) using six steel balls (350gm wt. and
50mm diameter each) continuously for a period of 8, 16 and
24 hours. The solid powder then obtained termed as organic
in-organic hybrid precursor characterized by X-ray diffrac-
tion analysis for identification of mineralogical phases, 29 Si
MAS NMR and 27 Al MAS NMR to determine connectiv-
ities of Si and Al and their coordination environment in
the developed solid geopolymeric precursor which enabled
us to confirm the presence of geopolymeric characteristics.
The microstructure and size of nano particles of tailored
hybrid precursor material for different grinding duration
were examined by SEM and FESEM analysis.
2.2 Characterization of Hybrid Geopolymeric
Precursor Material
XRD patterns of the solid powder obtained after
mechanochemical grinding at different hours recorded using
RIGAKU X-ray Diffractometer, at CSIR-AMPRI, Bhopal
(M.P.) India with operating conditions included continu-
ous scanning in angular range of 5°-70◦ with scan rate of
2 degree/minute using copper- K-alpha radiations, wave-
length 0.15 nm. JCPDS data used for analyzing the recorded
patterns.
Solid state 27 Al MAS NMR and 29 Si MAS NMR studies
of hybrid geopolymeric powder carried out at CSIR-
National Chemical Laboratory, Pune, Maharashtra, India
using JEOL ECX 400 MHz instrument, standard bore,
and probe-4 mm broad band with 4mm zirconia rotor.
Measurement conditions for 29 Si NMR included no. of
scans- 11000, relaxation delay-5secs and pulse rate ∼45
degree and for 27 Al NMR measurement conditions included
no. of scans-3000 and relaxation delay-4secs with same
pulse length. Microstructure of powder was determined
by subjecting the sample to SEM analysis; model- JOEL-
JSM-5600 and particle size of the developed powder
was determined by Field Emission Scanning Electron
Microscope (FESEM), model NOVA NANOSEM-430 of
COMFEI at CSIR-AMPRI, Bhopal, Madhya Pradesh, India.
2.3 Mechanical Property Testing
Later, by addition of only water to solid precursor material
[water to precursor ratio 0.21, 12.5M], organic in-organic
hybrid geopolymer formed which then subjected to mechan-
ical strength testing by casting mortar cubes [material to
sand ratio 1:3] of the three different hours grinded mate-
rial at various curing ages i.e. 3, 7, 14, 21 and 28 day.
The mortar cubes were oven cured at 60 ◦ C for 24 hours
in hot air oven and hardened cubes then demolded (after
1 day) to allow ambient curing until the time of testing.
The compressive strength were measured on cubic samples
of dimension 7.06 x 7.06 x 7.06 cm3 . HEICO compressive
strength testing machine [at CSIR-AMPRI] was employed
with 2.9KN/sec load Values reported in MPa. which are the
average of testing of three cubes at a time.
2.4 Microstructural Study of Organic In-Organic
Hybrid Geopolymer
The mortar sample of organic in-organic hybrid geopolymer
subjected to microstructural analysis to investigate the
compatibility of rice husk with the geopolymeric matrix and
to understand the effect on geopolymeric gelation due to
its hybrid character. Microscopic images of the eight hours
ground geopolymeric sample at different magnification
were acquired by SEM [model JOEL-JSM-5600 at CSIR-
AMPRI] in order to determine morphology of organic
in-organic hybrid geopolymer.
3 Results and Discussion
3.1 XRD Analysis
XRD pattern of organic in-organic hybrid tailored precur-
sors after 8, 16 and 24 hours of grinding duration are shown
in Fig. 2. Table 1 presents the different XRD phases corre-
sponding to tailored hybrid inorganic geopolymeric precur-
sor identified after 8, 16 and 24 hours of grinding duration

Fig. 2 XRD spectra of hybrid geopolymeric precursor at 8 hours
grinding, 16 hours grinding and at 24 hours grinding durations
using JCPDS software. The XRD results were compared
with XRD of as received coal fly ash which has also been
discussed and explained in our previously published study
[22] and depicted in Fig. 3.
Results revealed that the tailored solid precursor powder
basically consist of a major vitreous phase, (halo registered
around 2θ = 15◦ to 2θ =20°) which indicate the glassy reac-
tive fraction of fly ash and actively participated in geopoly-
merization reaction. The major crystalline phases in all three
XRD patterns recorded as sharp peaks between 2θ =18-70°.
The main crystalline constituents in the tailored precur-
sors included minerals such as quartz SiO2 (Silicon oxide,
Cat no.02-0458, major peaks with‘d’ values 3.35, 1.37,
1.54), mullite 3Al2 O3 .2SiO2 (Aluminium silicate, Cat no.-
02-0452, major peaks with‘d’ values 3.36, 2.20, 1.27) and
hematite Fe2 O3 (Iron oxide, Cat no.-01-1053, major peaks
with‘d’ values 2.69, 184, 1.69) which were also present in
XRD patterns of unground fly ash [22]. In addition to these
crystalline phases, new phases formed due to solid state
Table 1 XRD phases corresponding to hybrid solid geopolymeric precursors identified through PCPDFWIN software for three different grinding
hours
Geopolymeric precursor phases detected Chemical formula
Quartz SiO2
Mullite 3Al2 O3 .2SiO2
Hematite Fe2 O3
Sodium aluminium oxide NaAl6 O9.5
Sodium aluminium silicate Na39.8 Al70 .4 Si41.20207.9
Sodium silicate Na2 Si3 O7
Sodium aluminium silicate hydrate NaAlSiO2 O6 .3H2 O
α−D-glucose C6 H12 O6
Silicon
chemical reactions of glassy silicoaluminous phase from fly
ash and sodium hydroxide include NaAl6 O9.5 (Sodium Alu-
minium Oxide, Cat no.-47-0320, major peaks with‘d’ values
3.41, 5.40, 2.22), NaAlSiO2 O6 .3H2 O (Sodium Aluminium
silicate hydrate, Cat no.-19-1178, major peaks with‘d’
values 2.93, 4.32, 9.36), Na2 Si3 O7 (Sodium Silicate,
Cat no.-38-0019, major peaks with‘d’ values 3.38, 3.44,
3.84), Na39.8 Al70 .4 Si41.20207.9 (Sodium Aluminium Silicate,
Cat no.-47-0356, major peaks with‘d’ values 2.92, 3.68,
9.48).Another minor phase observed in the XRD spectra of
all three solid powder samples wasC6 H12 O6 (α-D-glucose,
Cat no.-24-1964, major peaks with‘d’ values 4.29, 3.13,
6.04), which originated by depolymerization of hemicel-
luloses due to continuous grinding of the parent material
rice husk. XRD data revealed that the solid state reactions
between fly ash, sodium hydroxide and rice husk form tai-
lored organic in-organic hybrid geopolymeric precursors
which require just addition of water alone to form geopoly-
mers. Presence of organic α-D-glucose provided an addi-
tional hybrid character and ultimately results in improved
mechanical and physical properties of geopolymeric end
product.
The patterns of three types of powder samples showed
the same crystalline phases from parent material i.e. fly
ash but with variable peak intensities for different grinding
hours. This could be explained as effect of grinding hours
on crystallinities of phases and amorphization of material.
When the XRD spectra of sample after 8 and 16 hours
grinding compared, it could be seen that there is marginal
increase in the peak intensities with increase in grinding
duration from 8 to 16 hours (35-70°2θ). The most relevant
deduction drawn from the diffractogram of samples from
grinding duration 8 to 24 was increase of intensities of peaks
of quartz, mullite and hematite, but significant intensity
increase observed on increasing grinding duration to 24
hours clearly indicated the consumption of glassy phase in
formation of geopolymeric precursors.
It is also observed from XRD spectras that the intensities
of newly formed phases gradually increase from 8 to 24
Strongest line at ‘d’ spacing (°A) Cell parameters
3.35 a=4.403, c=5.393
3.36 a=7.52, b=7.65, c=2.89
2.69 a=5.028, c=13.73
3.41 a=7.640, b=7.640, c=2.937
2.92 –
3.38 a=6.02, b=4.68, c=20.30
2.93 a=13.79, c=15.10
4.29 a=10.36, b=14.85, c=4.980
Silicon
Fig. 3 XRD spectra of
unground fly ash
hours grinding duration as confirmed by more number of
peaks of Na2 Si3 O7, NaAl6 O9.5 andNa39.8 Al70 .4 Si41.20207.9
in hybrid precursor material. Consequently, glassy phases
in fly ash dissipated to react with sodium hydroxide and
organic moieties and amorphous silica of rice husk as an
effect of mechanochemical grinding, forming new class
of inorganic and organic phases termed as geopolymeric
precursors with extreme fineness and the increased particle
surface area render the hybrid precursor material highly
reactive to form geopolymeric gel on just addition of water
with great homogeneity and improved texture [23, 24].
The reactive silica content of rice husk also governs
the geopolymeric properties desired for the end application
of the geopolymeric product. Amorphous silica from the
outer surface of rice husk mechanochemically activated
after prolonged grinding period possibly resulted increase
reactive silica content in the solid precursor material.
In the hybrid geopolymeric precursor, as the grinding
duration increased from 8 to 24 hours, intensities and
peaks of C6 H12 O6 increased, indicate the participation of
hemicelluloses from rice husk. Cellulose and hemicellulose
fractions of rice husk, are polymers of sugars, which
rapidly hydrolyzed in presence of mild acid/alkali [25].
As the mechanochemical grinding process proceeded in
dry environment, depolymerization of hemicelluloses due
to mechanical action took place to form constituent
glucose molecules with increasing intensities for successive
grinding hours. It is worthy to note that 24 hours grinding
duration resulted in marginal increase in amorphization
and more intensities of formed precursor compounds
than 8 and 16 hours ground samples. When the spectral
peaks appeared in hybrid precursor samples obtained after
grinding duration of 8 and 16 hours were compared, one
new peak for precursor obtained after 16 hours recorded
with d value=2.68 and 2θ =33.360◦ corresponding to
Na2 Si3 O7 and C6 H12 O6 whereas intensities of rest of the
peaks remained more or less similar for both 8 and 16 hours
grinding durations. It is observed from the XRD patterns
of precursor sample for 8, 16 and 24 grinding duration
that intensities correspond to recorded inorganic phases
and organic phase vary marginal as moving from 8-24
hours grinding through which it is conveniently concluded
that 8 hours mechanochemical grinding is sufficient to
induce activation of raw material to form tailored organic
in-organic hybrid geopolymeric precursors for making
advanced geopolymers with varying applications.
Thus, from the XRD data it is concluded that that
together mechanochemical grinding stimulated the solid
state chemical reactions between fly ash, rice husk and
sodium hydroxide resulting in breaking of old bonds and
formation of new ones under the continuous mechanical
pressure for different durations. Deformations and dis-
orderness in the crystalline structures due to continuous
mechanical milling render the particles highly reactive and
unstable form to react rapidly with the surrounding chemical
environment.
X-ray amorphous aluminosilicate gel (Si-O, Al-O),
fraction of fly ash, reacted with sodium hydroxide and silica
from rice husk to yield compounds like sodium aluminium
oxide, sodium silicate and sodium aluminium silicate which
possessed glassy nature. However it is an interesting matter
to study further about the stoichiometric ratios of reactants
(Si, Al and Na) consuming and new products forming
during the solid state transformations. It is to be noted
that all compounds were formed at ambient temperature
under mechanical pressure, hence in the current process, no
temperature regime is required for reactions to occur in solid
state.
3.2 29 Si and 27 Al MAS NMR Analysis
The 29 Si MAS NMR and 27 Al MAS NMR of unground
fly ash is presented in Fig. 4 whereas spectra of solid
hybrid geopolymeric precursor for different grinding hours
are presented in Figs. 5 and 6 respectively. NMR analysis is
always being a key factor in characterizing geopolymers as
it provides direct information about the coordination status
of silica and alumina units in their structure [26–28]. As
from Fig. 4, it is clearly indicated that spectra of unground
fly ash contain one resonating peak at δ -106.087 ppm in

Fig. 4 29 Si and 27 Al MAS
NMR spectra of unground fly
ash sample
29 Si MAS NMR which is attributed to starting vitreous
material in fly ash containing amorphous silica and two
resonating broad peaks at 45.644 and -7.132 ppm in 27 Al
MAS NMR corresponds to Al in tetrahedral coordination
AlQ4 (4Si) units to Al in octahedral coordination. These
resonances in fly ash spectra indicated the presence of
mullite and glassy phases in the fly ash.
The 29 Si NMR of hybrid geopolymer precursor exhibited
three broad asymmetric shoulders at δ-85.63 ppm, δ-98.97
ppm and δ-105.28 ppm at 8 hours of grinding. The peaks
originated in 29 Si NMR at δ-85.63 ppm corresponds to
SiQ2 , δ-98.97 pm corresponds to SiQ3 andSiQ4 (mAl)
coordination geometry of silica. These notations describe
the connectivity of a silicon tetrahedron which are bridged
through oxygen to aluminium atoms, where m ≤ 4. The
signals centered at δ-98.97 ppm, δ-94 ppm and δ-93 ppm
Fig. 5 29 Si MAS NMR
spectrum of solid hybrid
geopolymeric precursor
developed via solid state route
Silicon
(see Fig. 5) reflecting the incorporation of Al into Si
coordination sphere for hybrid precursor obtained after 8,
16 and 24 hours grinding duration respectively. Similarly,
the signals centered at δ-84ppm for grinding duration of 16
and 24 hours of grinding indicated four fold coordination
geometry around silica atom [29]. Also the resonances
between δ-84 ppm to δ-94 ppm in tailored hybrid precursors
obtained after 8,16 and 24 hours of grinding durations
indicate that raw materials were not fully reacted to form
geopolymers and present in the form of active precursors
only with tetrahedral coordination. These peaks results from
unreacted silicate oligomers present in the hybrid solid
precursors originated because of together mechanochemical
grinding that further bound to the gel when water added
externally for the geopolymerization process [30]. The low
level of SiQ0 and SiQ1 in all ground samples suggested that
Silicon
Fig. 6 27 Al MAS NMR
spectrum of solid hybrid
geopolymeric precursor
developed via solid state route
the signals resulting from the amorphous silicoaluminous
phase of fly ash has been largely diminished. This fact was
compatible and agreed well with the XRD results as the
amorphous silicoaluminous phase has been consumed in
the formation of new amorphous geopolymeric precursor
phases during mechanochemical grinding or the signal
intensity for SiQ0 and SiQ1 were significantly low because
of disruption of silica network resulting from the continuous
mechanochemical grinding for prolonged hours.
In the present study, the most significant finding of the
29 Si MAS NMR spectra of solid organic in-organic hybrid
geopolymeric precursor is the occurrence of pentavalent
silicon atoms along with tetravalent geometry, confirmed
through signals centered at δ-105 ppm for 8 and 16 hours of
grinding and δ-103 ppm for 24 hours of grinding duration
[31, 32]. The low level intensities at δ-103 ppm and δ-
105 ppm in 29 Si NMR spectra at different grinding hours
suggested that pentavalent silicon component present in the
samples is low. This result is supported by the fact that
complete transformation of tertracoordinated geometry of
silicon to pentacoordinated silicon is not possible without
the presence of aqueous alkaline medium.
The hypercoordinated silicon atom cause the bond
lengthening which is a well-known fact in silicon chemistry.
This hypercoordinated silica atom is highly reactive in
nature and immediately form silanols [Si (OH)]species
and further silanols react with other silanols to form
highly stable siloxane (-Si-O-Si-) bonds either when water
adsorbed on the surface or when it will react with water
molecules. The conventional geopolymerization reaction
proceeds in presence of hydroxyl groups (-OH) provided
by aqueous solution of alkali (via solution chemistry) [33].
On the contrary, in the current study, the hydroxyl groups
emerged during continuous mechanochemical grinding
of sodium hydroxide (-Na+ , -OH− ) and it is the key
solid state chemistry that allowed the formation of
geopolymeric precursors in solid powder form with
improved functionality and reactivity. The formation
and confirmation of pentacoordinated intermediate of
silicon atom in 29 Si NMR spectra was responsible
for imparting fascinating functionality in the hybrid
geopolymeric precursor molecules which ultimately lead
to improved compressive strength of the geopolymeric
end product. It is worthy to note that the bond length
of tertracoordinated silicon is short (1.62°A) as compared
to pentacoordinated silicon (1.71°A) [34]. This significant
lengthening of bond create excellent reactivity site for
silicon atom to react rapidly with coming hydroxyl ions
from water to form geopolymeric gel more rapidly than the
conventional geopolymerization process.
The presence of organic group i.e.C6 H12 O6 in the
precursor imparted hypercoordination to silicon atom.
Several reports on silicon chemistry demonstrated the
occurrence of pentavalent silica complexes with aliphatic
diols and other organic groups [35, 36].This firmly led to the
important speculation from this study that organic groups
from rice husk were involved in transforming tetravalent
geometry of silicon to pentavalent geometry shown as peaks
centered at δ-105ppm for 8 hours grinding and δ-103 ppm
for 16 and 24 hours grinding durations in 29 Si NMR spectra.
27 Al MAS NMR spectra of tailored hybrid precursor
consist of fly ash, rice husk and sodium hydroxide in solid
powder form for 8, 16 and 24 hours grinding is presented
in Fig. 6. Two broad NMR signals reported at δ52 ppm
and δ 66 ppm for 8 hours grinding and δ54 ppm and δ
68 ppm for 16 and 24 hours grinding durations indicated
the four coordinated Al in silicoaluminates [37]. It has
previously been reported by Davidovits and others that 27 Al
 Silicon

NMR peak at about 55±20 ppm indicates the conversion of
Al to fully tetravalent geometry with four oxygen atoms.
According to these studies, peak at approx. δ 55ppm in
27Al NMR spectra is exclusively needed to be called the
product a geopolymer [37–39]. The 27 Al NMR results
of the current study concluded that the solid precursor
material formed has geopolymeric characteristics confirmed
by signals originated in spectra between δ 52ppm to δ68
ppm. Hence based on the NMR results, the developed solid
precursor powder by solid state route can be appropriately
termed as hybrid geopolymeric precursor.
3.3 Particle Size and Microstructural Analysis
of Hybrid Geopolymeric Precursor
In this study, particle size of unground fly ash particles
and mechanochemically grinded organic in-organic hybrid
geopolymeric precursor powder obtained through SEM and
FESEM micrographs respectively. From Fig. 7a it is clear
that fly ash particles when unground show glassy, hollow
and spherical particles of approx. size around 7±4 µm. This
appearance of fly ash microstructure agree well with that
previously reported by Davidovits and other researchers

Fig. 7 Micrographs showing

particle size a SEM of fly ash
particles, b SEM of hybrid
geopolymeric precursor material
(area encircled showing
initiation of solid state reactions
on fly ash particle) c FESEM of
hybrid precursor at 8 hours
duration, d at 16 hours grinding
duration and e at 24 hours
grinding duration showing
differences in particle size
Silicon
[40–42]. From fly ash micrograph, it was observed that
particle shape of original fly ash is essentially uneven
(rounded to oval) with smooth texture and surface. On
the other hand, Fig. 6b is showing micrograph of the
geopolymeric precursor material under SEM analysis. The
effect of grinding could be easily seen from the micrograph
of geopolymeric precursor material. The hollow spherical
particles due to continuous mechanochemical grinding
effect significantly became rough and with unsmooth
surface. Also by detailed examination of the micrograph,
initiation of solid state reactions and formation of new
reaction products were observed which were not seen in
fly ash micrograph (see Fig. 7b). Although more detailed
analysis was not possible at this magnification but the result
obtained from SEM micrograph are in well agreement with
our XRD results.
The particle sizes of solid hybrid geopolymeric precursor
for 8, 16 and 24 hours duration are shown in Fig. 7c,
d and e respectively analyzed with the help of FESEM.
For 8 hours ground sample the particle size found in the
range of 40.9-77.4 nm. The size of hybrid precursor sample
powder after continuous 16 and 24 hours mechanochemical
grinding duration found in the range of 28-40 nm and
23- 29 nm respectively. Increase in grinding durations is
responsible for the particle size reduction and increased
fineness of fly ash particles. It is noteworthy that particle
size decreased from microns to nano meters after continuous
grinding for different hours. However, after increasing the
duration beyond 24 hours for mechanochemical grinding,
no significant particle size reduction observed. For all three
grinding durations, the particle size ranged in nanometers
but comparatively small sized particles with narrow size
distribution were observed in hybrid precursor sample
obtained after grinding duration of 24 hours i.e. in the range
of 23-29 nm. From this observation it is also concluded that
the minimum particle size of mechanochemically grinded
Fig. 8 Variation in compressive
strength of organic in-organic
hybrid geopolymer for five
Compressive strength (MPa)
different curing durations.
(Polynomial trendline used for
8h grinding duration)
hybrid geopolymeric precursor powder are in the range of
20-30 nm.
Nano size inorganic phases of Na2 Si3 O7, NaAl6 O9.5 ,
Na39.8 Al70 .4 Si41.20207.9 and organic phase of C6 H12 O6 (as
also confirmed by XRD) ultimately rendered the precursor
material highly reactive, with increase surface area and
varying reaction sites to enhance amorphous nature and
reactivity which promotes geopolymerization reaction.
3.4 Mechanical Strength Testing
Figure 8 shows the variation in compressive strength
with respect to different curing periods for 8, 16 and
24 hours ground organic in-organic hybrid geopolymeric
samples. Similar to conventional geopolymer cement
system, the strength gain reported maximum for 28 day.
When compared with the conventional geopolymer strength
[22], it is found that strength of 8, 16 and 24 hours
ground material increased. Noteworthy, there was no
disagreement between the results of compressive strength
and characterization as no much variation in strength
was noticeable from the graph and at all curing ages.
Eight hours ground hybrid geopolymeric material showed
desired compressive strength when compared to 16 and 24
hours ground hybrid geopolymeric material. This trend in
measurement of compressive strength suggested that dry
grinding of raw materials for 8 hours produced sufficient
reactivity and amorphization as also indicated by XRD
results and particle size analysis by FESEM. The reported
maximum compressive strength is 32.9 M.Pa. for 24
hours ground hybrid geopolymer which was insignificantly
different from the strength of 8 hours ground hybrid
geopolymer- 32.5 M.Pa. The strength of geopolymer is
strongly affected by variation in Si/Al ratio and Na/Al
ratio, as these factors kept constant in this study, the
results elucidated the fact that hybrid inorganic and organic
y = -0.0929x2 + 3.1071x + 18.58
40
R² = 0.9362
35
30
25
20
15
10
5
0
3 7 14 21 28
Curing periods (days)

characters and together mechanochemical grinding of raw
materials resulted into increase in compressive strength
of the material. As we claimed in our previous text,
after together mechano- chemical grinding the organic
fractions and inorganic silica from rice husk provided
extreme homogeneity and compact gelation as clearly
seen during preparation of geopolymeric material for
strength testing and also promoted the chemical reactions
during geopolymerization. The results of strength testing
strengthened the fact that organic fraction from rice
husk significantly governs the homogenous nature, even
distribution of Si/Al and compact gelation process. The
relationship between strength and grinding hours again
suggested that 8 hours grinding is optimum to achieve good
mechanical strength.
3.5 Microstructural and Morphological Study
of Hybrid Geopolymeric Material
Being optimized from previous results, organic in-organic
hybrid geopolymer then subjected to microstructural and
morphological study and the micrographs at two differ-
ent magnification are displayed in Fig. 9. Typically, the
matrix of geopolymer contain spherical or oval particles of
dimension 10±5 µm. The geopolymeric gel matrix presented
strong bonding with rice husk particles and appears to
exhibit homogenous structure at the microscale. Upon addi-
tion of water to hybrid geopolymeric precursor, geopoly-
merization process continued and slightly less raw mate-
rials remain unreacted as seen in the micrographs. Also
addition of water to hybrid geopolymeric precursor lead
to formation of densified, smooth textured geopolymeric
gel with the incorporation of rice husk into the matrix.
The rice husk relicts found to be randomly distributed in
the matrix; compatible with the Si/Al phase; and impart
enhanced gelation due to discharge of organic fractions
from its composition. The compact and smooth appearance
of geopolymeric matrix in the micrographs suggested the
Fig. 9 Microstructure and
morphology of organic
in-organic hybrid geopolymeric
material indicating compact
gelation and rice husk relicts
into the geopolymeric matrix
Silicon
more intervening Si-O-Al framework during solidification
process which result in the development of better mor-
phology and microstructure for better mechanical strength.
Further, the absence of microcracks in the morphology
is manifestation of grinding effect on geopolymerization
reactions. In short, from this study, we can conclude that
prolonged mechanochemical co-grinding and hybrid char-
acters from rice husk plays important role in geopolymeric
microstructure and mechanical strength.
4 Conclusions
Advanced geopolymeric precursor material having hybrid
character is developed by novel risk free solid state synthesis
route utilizing two waste materials and characterized using
sophisticated instrumental techniques. Hybrid precursor
require addition of water alone to form advanced geopoly-
meric material and ultimately offers a user-friendlier
approach for manufacture of different geopolymeric prod-
ucts. Some other important conclusions drawn from the
study are listed below:
1. Remarkable effect of mechanochemical grinding for
three different grinding duration (8, 16 and 24 hours)
was observed on the amorphous nature of raw materials.
Sufficient amorphization was induced at 8 hours
grinding duration.
2. XRD analysis confirmed the formation of five new
phases of geopolymeric characteristics via prolonged
mechanochemical grinding. XRD results were in good
agreement with 29 Si MAS NMR and 27 Al MAS NMR
spectra.
3. 29 Si MAS NMR spectra of solid hybrid geopolymeric
precursor indicated presence of pentavalent silicon
atoms along with tetravalent silicon atoms.
4. 27 Al MAS NMR spectra of the solid precursor materials
indicated presence of NMR signals between δ 52ppm to
δ 68 ppm exhibited geopolymeric characteristics.
Silicon
5. FESEM analysis for three varying grinding duration
revealed the presence of nanosized particles (between
23-77.4 nm) for developed hybrid precursors. Nanosize
of particles decreased with increase in grinding
duration.
6. Rice husk functioned as source of inorganic silica
and organic components as well to impart continu-
ous growth of Si-O-Al polymeric chain, leading to
densified, strong, homogeneous geopolymeric matrix
essential for excellent engineering performances.
7. Mechanical strength results of hybrid geopolymer are
in agreement with results of characterization studies
and microstructural analysis of hybrid geopolymeric
material indicated occurrence of better morphology
which imparts better mechanical strength.
8. Solid state chemical route was found to be a novel
and user friendly approach as compared to conventional
geopolymerization process via solution chemistry, so as
to overcome its existing drawbacks and to ensure broad
application spectrum.
Acknowledgements Authors of this paper are highly grateful to
Director, CSIR-AMPRI for his kind support to carry out this work
successfully. Authors are also thankful to CSIR-NCL, Pune, for
providing NMR facility for this work. A special gratefulness to
Dr.O.P.Modi, Mohd.Shafeeq and Deepak Kashyap for their help
in performing X-ray diffraction and Scanning electron microscopic
studies.
Compliance with Ethical Standards
Conflict of interests Authors of this research declare no conflicts of
interest.
References
1. Gomez-Alcantara MM, Cabeza A, Aranda MAG, Guagliardi A,
Mao JG, Clearfield A (2004) Synthesis and characterization of
metal carboxyalkylphosphonates hybrid materials. Solid State Sci
6:479–487
2. Mucsi G, Kumar S, Csoke B et al (2015) Control of geopolymer
properties by grinding of land filled fly ash. Int J Miner Process
143:50–58
3. Fansuri H, Prasetyoko D, Zhang Z, Zhang D (2012) The effect
of sodium silicate and sodium hydroxide on the strength of
aggregates made from coal fly ash using the geopolymerization
method. Asia-Pac J Chem Eng 7:73–79
4. Davidovits J (2011) Geopolymer chemistry and application.
Published by, Institut Geopolimere, 16 rue Galilee F-02100 Saint-
Quentin France (ISBN: 9782951482050)
5. Catauro M, Bollino F, Papale F, Lamanna G (2014) Investigation
of the sample preparation and curing treatment effects on
mechanical properties and bioactivity of silica rich metakaolin
geopolymer. Mater Sci Eng C 36:20–24
6. Komljenovic M, Bascarevic Z, Bradic V (2010) Mechanical and
microstructural properties of alkali-activated fly ash geopolymers.
J Hazard Mater 181(1–3):35–42
7. El-Gamal SMA, Selim FA (2017) Utilization of some industrial
wastes for eco-friendly cement production. Sustain Mater Technol
12:9–17
8. White CE, Provis JL, Proffen T, Deventer JSJV (2010) The
effect of temperature on the local structure of metakaolin-
based geopolymer binder: a neutron pair distribution function
investigation. J Amer Ceram Soc 93(10):3486–92
9. Lizcano M, Gonzalez A, Basu S et al (2010) Effects of water
content and chemical composition on structural properties of
alkaline activated metakaolin-based geopolymers. J Amer Ceram
Soc, 1–9
10. White CE, Provis JL, Llobet A et al (2011) Evolution of local
structure in geopolymer gels: an in sity neutron pair distribution
function analysis. J Amer Ceram Soc 94(10):3532–3539
11. Nematollahi B, Sanjayan J, Shaikh F (2015) Synthesis of heat and
ambient cured one-part geopolymer mixes with different grades of
sodium silicate. Ceram Int 41(4):5696–5704
12. Ke X, Bernal S, Ye N et al (2015) One-part geopolymers based
on thermally treated red mud/NaOH blends. J Amer Ceram Soc
98(1):5–11
13. Hajimohammadi A, Provis JL, Jannie S, van Deventer J (2008)
One-part geopolymer mixes from geothermal silica and sodium
aluminate. Indus Eng Chem Res 47:9396–9405
14. Yang K, Song J (2009) Workability loss and compressive strength
development of cementless mortars activated by combination
of sodium silicate and sodium hydroxide. J Mater Civ Eng
21(3):119–127
15. Ferone C, Roviello G, Colangelo F et al (2013) Novel hybrid
organic-geopolymer materials. Appl Clay Sci 73:42–50
16. Hussain M, Varley RJ, Cheng YB, Simon GP (2004) Investigation
of thermal and fire performance of novel hybrid geopolymer
composites. J Mater Sci 39:4721–4726
17. Hussain M, Varley RJ, Cheng YB et al (2005) Synthesis
and thermal behavior of inorganic–organic hybrid geopolymer
composites. J Appl Polym Sci 96:112–121
18. Takahashi H (1959) Effects of dry grinding on kaolin minerals. II,
Kibushi-clay
19. Zaldivar-Cadena AA, Diaz-Pena I, Gonzalez-Lopez JR et al
(2013) Effect of milling time on mechanical properties of fly ash
incorporated cement mortars. Adv Mater Res 787:286–290
20. Temuujin J, Williams RP, vanRiessen A (2009) Effect of
mechanical activation of fly ash on the properties of geopolymer
cured at ambient temperature. J Mater Process Techno 209(12–
13):5276–5280
21. Hela R, Orsakova D (2013) The mechanical activation of fly ash.
Procedia Eng 65:87–93
22. Gupta R, Bhardwaj P, Mishra D, Mudgal M, Chouhan RK, Prasad
M, Amritphale SS (2017) Evolution of advanced geopolymeric
cementitious material via a novel process. Adv Cement Res
29(3):125–134
23. Intini G, Liberti L, Notarnicola M, Di Canio F (2009)
Mechanochemical activation of coal fly ash for production of high
strength cement. Chem Sustain Develop 17:557–561
24. Yazici S, Arel HS (2012) Effects of fly ash fineness on the
mechanical properties of concrete. Sadhana Indian Aca Sci Part
37(3):389–403
25. Harmsen PHF, Huijgen WJJ, Berbudez Lopez LM, Bakker RRC
(2010) Literature review of physical and chemical pretreatment
process for lignocellulosic biomass. Bioenergy
26. Duxson P, Provis JL, Lukey GC et al (2005) Understanding
the relationship between geopolymer composition, microstructure
and mechanical properties. Colloids Surf A: Physicochem Eng
Aspects 269:47–58
27. Urbanova M, Kobera L, Brus J (2013) Factor analysis of 27 Al
MAS NMR spectra for identifying nanocrystalline phases in
amorphous geopolymers. Magn Reson Chem 51:734–742

28. Azizi SNTilami SE (2009) Theoretical and experimental 27Al
NMR chemical shift studies on end-group aluminates linked to
different silicate species. J Chinese Chem Soc 56:898–907
29. Zhang B, MacKenzie KJD, Bigley C, Ryan MJ, Brown IWM
(2009) Phase development of NaOH activated blast furnace slag
geopolymers cured at 90◦ C. AIP Conf Proc 1151(1):44–47
30. Duxson P, Provis JL, Lukey GC et al (2005) 29 Si NMR study
of structural ordering in aluminosilicate geopolymer gels. ACS
Langmuir 21(7):3028–3036
31. Devi J, Batra N, Kumari S (2011) Synthesis and characterization
of novel organosilicon (IV) complexes with pyridine dicarboxylic
acid and mercaptopuridinecarboxylic acid. Int J Res Chem
Environ 1(2):50–56
32. Jitchum V, Chivin S, Wongkasemjit S, Ishida HV (2001)
Synthesis of spirosilicates directly from silica and ethylene
glycol/ethylene glycol derivatives. Tetrahedron 57(18):3997–4003
33. Organosilane Technology in Coating Applications: Review and
Perspectives, http://www.dowcorning.com/content/publishedlit/
26-1402-01.pdf
34. Sahai N, Tossell JA (2001) Formation energies and NMR chemical
shifts calculated for putative serine-silicate complexes in silica
biomineralization. Geochimica Cosmochimica Acta 65(13):2043–
2053
Silicon
35. Oscar J, Halla CJ, Robles J et al (2006) Theoretical and
experimental study on a spirocyclic diethyleneglycol silicon
complex. J Mexican Chem Soc 50(4):184–195
36. Waglera J, Ohmea UB, Brendlerb E, Roewer G (2004) First x-
ray structure of a cationic silicon complex with salen-type ligand:
an unusual compound with two different Si-N dative Bonds. Z
Naturforsch 59b:1348–1352. http://znaturforsch.com
37. Nasab GM, Golestanifard F, MacKenzie KJD (2014) The effect of
the SiO2 /Na2 O ratio in the structural modification of metakaolin-
based geopolymers studied by XRD, FTIR and MAS-NMR. J
Ceram Sci Technol 05(03):185–192
38. Davidovits J (1999) In: Proc. 2nd Intern. Conf. “Geopolymere
’99”. St. Quentin
39. Davidovits J (2005) In: Proc. World Congress “Geopolymer
2005”. St. Quentin
40. Davidovits J (2008) Geopolymer chemistry application. Institute
Geopolymer
41. Al Bakri AMM, Kamarudin H, Norazian MN, Ruzaidi CM,
Zarina Y, Rafiza AR (2011) Microstructure studies on the
effect of the alkaline activators ratio in preparation of fly ash-
based geopolymer. In: International conference on chemistry and
chemical process, Singapore, IPCBEE, vol 10
42. Liu Y, Yana C, Qiua X et al (2015) Preparation of faujasite block
from fly ash-based geopolymer via in-situ hydrothermal method. J
Taiwan Inst Chem Eng. https://doi.org/10.1016/j.jtice.2015.07.01